The invention relates to novel substituted thienocycloalk(en)ylamino-1,3,5-triazines, to processes for their preparation including the novel intermediates, and to their use as herbicides.
A number of substituted thienylalkylamino-1,3,5-triazines are already known from the (patent) literature (cf. WO-A-98/15537, WO-A-98/15539, DE-A-19744232). However, these compounds have hitherto not attained any particular importance. Substituted thienocycloalk(en)ylamino-1,3,5-triazines have hitherto not been disclosed at all.
This invention, accordingly, provides the novel thienocycloalk(en)ylamino-1,3,5-triazines of the general formula (I) 
in which
R1 represents hydrogen or represents optionally substituted alkyl,
R2 represents hydrogen, represents formyl or represents in each case optionally substituted alkyl, alkylcarbonyl, alkoxycarbonyl or alkylaminocarbonyl,
or the grouping N(R1R2) also represents dialkylaminoalkylideneamino,
R3 represents hydrogen, represents halogen, represents optionally substituted alkyl, represents in each case optionally substituted alkylcarbonyl, alkoxycarbonyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl, represents in each case optionally substituted alkenyl or alkinyl, or represents optionally substituted cycloalkyl, and
Z represents one of the thienocycloalk(en)yl groupings below 
xe2x80x83in which
m represents the numbers 0, 1, 2, 3 or 4,
n represents the numbers 0, 1 or 2,
A1 represents O (oxygen), S (sulphur), xe2x80x94COxe2x80x94, xe2x80x94CSxe2x80x94 or alkanediyl (alkylene),
A2 represents O (oxygen), S (sulphur), xe2x80x94COxe2x80x94, xe2x80x94CSxe2x80x94 or alkanediyl (alkylene),
A3 represents O (oxygen), S (sulphur), xe2x80x94COxe2x80x94, xe2x80x94CSxe2x80x94 or alkanediyl (alkylene),
with the proviso that at least one of the groupings A1, A2, A3 represents alkanediyl and that two adjacent groups do not simultaneously represent S or Oxe2x80x94
R4 represents amino, cyano, carbamoyl, thiocarbamoyl, formyl, halogen, or represents in each case optionally substituted alkyl, alkylcarbonyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkylcarbonylamino, alkoxycarbonylamino, alkylsulphonylamino, alkenyl, alkinyl, alkenylcarbonyl, alkinylcarbonyl, carbonyl, aryl arylcarbonyl or arylalkyl, and
R5 represents nitro, amino, cyano, carbamoyl, thiocarbamoyl, formyl, halogen, or represents in each case optionally substituted alkyl, alkylcarbonyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkylcarbonylamino, alkoxycarbonylamino, alkylsulphonylamino, alkenyl, alkinyl, alkenylcarbonyl, alkinylcarbonyl, aryl, arylcarbonyl or arylalkyl.
Saturated or unsaturated hydrocarbon groupings, such as alkyl, alkanediyl, alkenyl or alkinyl, arexe2x80x94including in combinations with heteroatoms, such as in alkoxyxe2x80x94in each case straight-chain or branched, as far as this is possible.
Optionally substituted radicals can be mono- or polysubstituted, where in the case of polysubstitution the substituents can be identical or different.
Preferred substituents or ranges of the radicals present in the formulae shown above and below are defined below.
m preferably represents the numbers 0, 1 or 2.
A1 preferably represents O (oxygen), S (sulphur), xe2x80x94COxe2x80x94, xe2x80x94CSxe2x80x94 or alkanediyl (alkylene) having 1 to 3 carbon atoms.
A2 preferably represents O (oxygen), S (sulphur), xe2x80x94COxe2x80x94, xe2x80x94CSxe2x80x94 or alkanediyl (alkylene) having 1 to 3 carbon atoms.
A3 preferably represents O (oxygen), S (sulphur), xe2x80x94COxe2x80x94, xe2x80x94CSxe2x80x94 or alkanediyl (alkylene) having 1 to 3 carbon atoms.
In the preferred compounds, at least one of the groupings A1, A2, A3 represents alkanediyl having 1 to 3 carbon atoms, and two adjacent groups do not simultaneously represent S or O.
R1 preferably represents hydrogen or represents optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl having 1 to 6 carbon atoms.
R2 preferably represents hydrogen, represents formyl or represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkylcarbonyl, alkoxycarbonyl or alkylaminocarbonyl having in each case 1 to 6 carbon atoms in the alkyl groups.
The grouping N(R1R2) preferably also represents dialkylaminoalkylideneamino having in each case up to 4 carbon atoms in the alkyl groups or alkylidene groups.
R3 preferably represents hydrogen, represents halogen, represents optionally cyano-, halogen-, hydroxyl-, C1-C4-alkoxy- or C1-C4-alkylthio-substituted alkyl having 1 to 6 carbon atoms, represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkylcarbonyl, alkoxycarbonyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups, represents in each case optionally halogen-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, or represents optionally cyano-, halogen- or C1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms.
R4 preferably represents amino, cyano, carbamoyl, thiocarbamoyl, formyl, halogen, represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkylcarbonyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkylcarbonylamino, alkoxycarbonylamino or alkylsulphonylamino having in each case 1 to 6 carbon atoms in the alkyl groups, represents in each case optionally cyano- or halogen-substituted alkenyl, alkinyl, alkenylcarbonyl or alkinylcarbonyl having in each case 2 to 6 carbon atoms in the alkenyl or alkinyl groups, or represents in each case optionally nitro-, cyano-, halogen-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy- or C1-C4-alkoxy-carbonyl-substituted aryl, arylcarbonyl or arylalkyl having in each case 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl moiety.
R5 preferably represents nitro, amino, cyano, carbamoyl, thiocarbamoyl, formyl, halogen, represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkylcarbonyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkylcarbonylamino, alkoxycarbonylamino or alkylsulphonylamino having in each case 1 to 6 carbon atoms in the alkyl groups, represents in each case optionally cyano- or halogen-substituted alkenyl, alkinyl, alkenylcarbonyl or alkinylcarbonyl having in each case 2 to 6 carbon atoms in the alkenyl or alkinyl groups, or represents in each case optionally nitro-, cyano:-, halogen-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy- or C1-C4-alkoxy-carbonyl substituted aryl, arylcarbonyl or arylalkyl having in each case 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl moiety.
A1 particularly preferably represents O (oxygen), S (sulphur), xe2x80x94COxe2x80x94, xe2x80x94CSxe2x80x94, methylene, dimethylene or trimethylene.
A2 particularly preferably represents O (oxygen), S (sulphur), xe2x80x94COxe2x80x94, xe2x80x94CSxe2x80x94, methylene, dimethylene or trimethylene.
A3 particularly preferably represents O (oxygen), S (sulphur), xe2x80x94COxe2x80x94, xe2x80x94CSxe2x80x94, methylene, dimethylene or trimethylene.
In the preferred compounds, at least one of the groupings A1, A2, A3 represents methylene, dimethylene or trimethylene, and two adjacent groups do not simultaneously represent S or O.
R1 particularly preferably represents hydrogen or represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl.
R2 particularly preferably represents hydrogen, represents formyl or represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylamino-carbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl.
The grouping N(R1R2) particularly preferably also represents dimethylaminomethyleneamino or diethylaminomethyleneamino.
R3 particularly preferably represents hydrogen, represents fluorine, chlorine, bromine, represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, hydroxyl-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, n- or i-propylthio-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy- substituted acetyl, propionyl, n- or i-butyroyl, methoxy-carbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethyl-sulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, represents in each case optionally fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, butenyl, ethinyl, propinyl or butinyl, or represents in each case optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
R4 particularly preferably represents amino, cyano, carbamoyl, thiocarbamoyl, formyl, fluorine, chlorine, bromine, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, acetyl, propionyl, n- or i-butyroyl, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propyl-sulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetylamino, propionylamino, n- or i-butyroylamino, methoxycarbonylamino, ethoxycarbonylamino, n- or i-propoxycarbonylamino, methylsulphonylamino, ethylsulphonylamino, n- or i-propylsulphonylamino, represents in each case optionally cyano-, fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, butenyl, ethinyl, propinyl, butinyl, ethenylcarbonyl, propenyl-carbonyl, butenylcarbonyl, ethinylcarbonyl, propinylcarbonyl or butinyl-carbonyl, or represents in each case optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, tri-fluoromethoxy-, methoxycarbonyl-, ethoxycarbonyl-, n- or i-propoxy-carbonyl-substituted phenyl, benzoyl or benzyl.
R5 particularly preferably represents nitro, amino, cyano, carbamoyl, thio-carbamoyl, formyl, fluorine, chlorine, bromine, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, acetyl, propionyl, n- or i-butyroyl, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxy-carbonyl, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethyl-sulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylamino, ethylamino, n- or i-propylamino, dimethyl-amino, diethylamino, acetylamino, propionylamino, n- or i-butyroylamino, methoxycarbonylamino, ethoxycarbonylamino) n- or i-propoxycarbonylamino, methylsulphonylamino, ethylsulphonylamino, n- or i-propyl-sulphonylamino, represents in each case optionally cyano-, fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, butenyl, ethinyl, propinyl, butinyl, ethenylcarbonyl, propenylcarbonyl, butenylcarbonyl, ethinyl-carbonyl, propinylcarbonyl or butinylcarbonyl, or represents in each case optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methoxycarbonyl-, ethoxy-carbonyl-, n- or i-propoxycarbonyl-substituted phenyl, benzoyl or benzyl.
A1 very particularly preferably represents methylene or dimethylene.
A2 very particularly preferably represents methylene or dimethylene.
A3 very particularly preferably represents methylene or dimethylene.
R2 very particularly preferably represents hydrogen.
R2 very particularly preferably represents hydrogen, represents formyl or represents in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxy-carbonyl, n- or i-propoxycarbonyl.
The grouping N(R1R2) very particularly preferably also represents dimethylaminomethyleneamino.
R3 very particularly preferably represents in each case optionally fluorine- or chlorine-substituted methyl, ethyl, n- or i-propyl.
R4 very particularly preferably represents cyano, fluorine, chlorine, bromine, or represents in each case optionally fluorine- or chlorine-substituted methyl, ethyl, methoxy or ethoxy.
R5 very particularly preferably represents nitro, cyano, fluorine, chlorine, bromine, or represents in each case optionally fluorine- or chlorine-substituted methyl, ethyl, methoxy or ethoxy.
In the general formula (I), Z most preferably represents 
where
p represents 2, 3 or 4 and n, m, R4 and R5 are as defined above.
The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with one another as desired, i.e. including combinations between the given preferred ranges.
Preference according to the invention is given to those compounds of the formula (I) which contain a combination of the meanings given above as being preferred.
Particular preference according to the invention is given to those compounds of the formula (I) which contain a combination of the meanings given above as being particularly preferred.
Very particular preference according to the invention is given to those compounds of the formula (I) which contain a combination of the meaning given above as being very particularly preferred.
Most preference according to the invention is given to those compounds of the formula (I) in which Z has the meaning given as being most preferred.
Saturated or unsaturated hydrocarbon radicals, such as alkyl, alkanediyl or alkenyl, ilk arexe2x80x94including in combination with heteroatoms, such as in alkoxyxe2x80x94in each case straight-chain or branched, as far as this is possible.
Optionally substituted radicals can be mono- or polysubstituted, where in the case of polysubstitution the substituents can be identical or different.
If appropriate, the compounds of the general formula (I) according to the invention contain an asymmetrically substituted carbon atom, in which case they can be present in different enantiomeric (R- and S-configured forms) or diastereomeric forms. The invention relates both to the various possible individual enantiomeric or stereoisomeric forms of the compounds of the general formula (I), and to the mixtures of these isomeric compounds.
The novel substituted thienocycloalk(en)ylamino-1,3,5-triazines of the general formula (I) have interesting biological properties. In particular, they have strong herbicidal activity.
The novel substituted thienocycloalk(en)ylamino-1,3,5-triazines of the general formula (I) are obtained when biguanides of the general formula (II) 
in which
R1, R2 and Z are as defined above,
and/or acid adducts of compounds of the general formula (II)
are reacted with alkoxycarbonyl compounds of the general formula (III)
R3xe2x80x94COxe2x80x94ORxe2x80x2xe2x80x83xe2x80x83(III)
xe2x80x83in which
R3 is as defined above and
Rxe2x80x2 represents alkyl,
if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent
and, if appropriate, further conversions within the scope of the definition of the substituents are carried out by customary methods on the resulting compounds of the general formula (I).
The compounds of the general formula (I) can be converted by customary methods into other compounds of the general formula (I) in accordance with the above definition of the substituents, for example by reacting compounds of the formula (I) in which R2 represents hydrogen with acylating agents, such as, for example, acetyl chloride, acetic anhydride, propionyl chloride, propionic anhydride, methyl chloroformate or ethyl chloroformate (in the case of R2 for example introduction of COCH3, COC2H5, COOCH3, COOC2H5 groups for a hydrogen atom).
Using, for example, 1-(4,5,6,7-tetrahydro-benzo[b]thiophen-4-yl)-biguanide and methyl trifluoroacetate as starting materials, the course of the reaction in the process according to the invention can be illustrated by the following formula scheme: 
The formula (II) provides a general definition of the biguanides to be used as starting materials in the process according to the invention for preparing compounds of the general formula (I). In the general formula (II), R1, R2 and Z preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the general formula (I) according to the invention, as being preferred or as being particularly preferred for R1, R2 and Z.
Suitable acid adducts of compounds of the formula (II) are their adducts with protic acids, such as, for example, with hydrogen chloride, hydrogen bromide, sulphuric acid, methanesulphonic acid, benzenesulphonic acid and p-toluenesulphonic acid.
The starting materials of the general formula (II) have hitherto not been disclosed in the literature; as novel substances, they also form part of the subject-matter of the present application.
The novel biguanides of the general formula (II) are obtained when amino compounds of the general formula (IV)
Zxe2x80x94NH2xe2x80x83xe2x80x83(IV)
in which
Z is as defined above,
and/or acid adducts of compounds of the general formula (IV), such as, for example, the hydrochlorides
are reacted with cyanoguanidine (xe2x80x9cdicyanodiamidexe2x80x9d) of the formula (V) 
xe2x80x83if appropriate in the presence of a reaction auxiliary, such as, for example, hydrogen chloride, and if appropriate in the presence of a diluent, such as, for example, n-decane or 1,2-dichloro-benzene, at temperatures between 100xc2x0 C. and 200xc2x0 C. (cf. the Preparation Examples).
The biguanides of the general formula (II) can, after their preparation, also be employed directly, without intermediate isolation, for preparing the compounds of the general formula (I) by the process according to the invention (cf. the Preparation Examples).
The amino compounds of the general formula (IV) required as precursors are known and/or can be prepared by processes known per se (cf. J. Org. Chem. 18 (1953), 1511-1515; JP-A-03223277xe2x80x94quoted in Chem. Abstracts 1992:128652 or 116:128652).
The amino compounds of the general formula (IV) are obtained when corresponding cyclic ketones (one of the radicals A1, A2 or A3 then representing xe2x80x94COxe2x80x94) are reacted with formamide at temperatures between 140xc2x0 C. and 190xc2x0 C., and the resulting formylamino compound is subsequently hydrolysed by heating with aqueous hydrochloric acid (cf J. Org. Chem. 18 (1953), 1511-1515), or when the corresponding cyclic ketones are initially, by reaction with hydroxylamine hydrochloride, if appropriate in the presence of a diluent, such as, for example, pyridine, at temperatures between 0xc2x0 C. and 50xc2x0 C., converted into corresponding oximes and these are then reacted with a reducing agent, such as, for example, sodium borohydride, in the presence of a reaction auxiliary, such as, for example, titanium (IV) chloride, and in the presence of a diluent, such as, for example, 1,2-dimethoxyethane, at temperatures between xe2x88x9220xc2x0 C. and +50xc2x0 C. (cf. the Preparation Examples).
The corresponding cyclic ketones are known and/or can be prepared by processes known per se (cf. J. Chem. Soc. 1953, 1837-1842; J. Heterocycl. Chem. 2 (1965), 44-48; loc. cit. 17 (1980), 87-92; loc. cit. 29 (1992), 1213-1217; J. Pharm. Sci. 52 (1963), 898-901; U.S. Pat No. 3,301,874).
The formula (III) provides a general definition of the alkoxycarbonyl compounds further to be used as starting materials in the process according to the invention for preparing compounds of the general formula (I). In the general formula (III), R3 preferably or in particular has that meaning which has already been mentioned above, in connection with the description of the compounds of the general formula (I) according to the invention, as being preferred or as being particularly preferred for R3; Rxe2x80x2 preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl.
The starting materials of the general formula (III) are known chemicals for synthesis.
The process according to the invention for preparing the compounds of the formula (I) is, if appropriate, carried out using a reaction auxiliary. Suitable reaction auxiliaries are, in general, the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide or potassium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide; furthermore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N,-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N,N-dimethyl-aniline, N,N-di-methyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4di-methylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo[2,2,2]-octane (DABCO), 1,5-diazabicyclo[4,3,0]-non-5-ene (DBN), or 1,8 diazabicyclo[5,4,0]-undec-7-ene (DBU).
The process according to the invention for preparing the compounds of the general formula (I) is, if appropriate, carried out using a diluent. Suitable diluents are especially inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; esters such as methyl acetate or ethyl acetate, sulphoxides, such as dimethyl sulphoxide, alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, mixtures thereof with water or pure water.
When carrying out the process according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the process is carried out at temperatures between 0xc2x0 C. and 150xc2x0 C., preferably between 10xc2x0 C. and 120xc2x0 C.
The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressurexe2x80x94in general between 0.1 bar and 10 bar.
In carrying out the process according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to employ a relatively large excess of one of the components. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary and the reaction mixture is generally stirred for a number of hours at the temperature required. Work-up is carried out by customary methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed-killers. By weeds in the broadest sense, there are to be understood all plants which grow in locations where they are not wanted. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindermia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicun, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera, Aegilops and Phalaris.
Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The active compounds according to the invention are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and railway tracks, and on paths and squares with or without tree plantings. Equally, the active compounds according to the invention can be employed for the control of weeds in perennial crops, for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, in lawns, turf and pasture-land, and for the selective control of weeds in annual crops.
The compounds of the formula (I) according to the invention have strong herbicidal activity and a broad activity spectrum when used on the soil and on above-ground parts of plants. To a certain extent, they are also suitable for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both pre-emergence and post-emergence.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foam formers.
If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents. Suitable liquid solvents are essentially the following: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are for example crushed fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifying and/or foam-forming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as protein hydrolysates; suitable dispersing agents are: for example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For the control of weeds, the active compounds according to the invention, as such or in their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example
acetochlor, acifluorfen(-sodium), aclonifen, alachor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azirmsulfuron, benazolin(-ethyl), benfuresate, bensulfuron(-methyl), bentazone, benzobicyclon, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bispyribac(-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentraione(-ethyl), chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen, chlorsulfuron, chlorotoluron, cinidon(-ethyl), cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop(-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron(-methyl), cloransularn(-methyl), curnyluron, cyanazine, cybutryne, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), diclosulam, diethatyl(-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epoprodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop(-P-ethyl), fentrazarnide, flamprop(-isopropyl), flamprop(-isopropyl-L), flamprop(-methyl), flazasulfuron, florasilam, fluazifop(-P-butyl), fluazolate, flucarbazone, flufenacet, flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurpyrsulfuron(-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr(-methyl), flurprimidol, flurtamone, fluthiacet(-methyl), fluthiamide, fomesafen, glufo-sinate(-ammonium), glyphosate(-isopropylammonium), halosafen, haloxy-fop(-ethoxyethyl), haloxyfop(-P-methyl), hexazinone, imazamethabenz-(-methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron(-methyl, -sodium), ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, mesotrione, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha-)metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfltorfen, -paraquat, pelargonic acid, pendimethalin, pendralin, pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, propanil, propaquizafop, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen(-ethyl), pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyriminobac-(-methyl), pyrithiobac(-sodium), quinchlorac, quimnerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thia-fluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfiron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.
A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, is also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by firther dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering,spraying, atomizing or scattering.
The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a relatively wide range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the following examples.